Magenta phenazonium dyestuff images from 6-substituted-8-hydroxyquinoline couplers



Patented Oct. 3., 1950 MAGENTA PHENAZONIUM DYESTUFF IMAGES FROM G-SUBSTITUTED-S-HY- DROXYQUINOLINE COUPLERS Vsevolod Tulagin, Phillipsburg, N. .-I., and Robert F. Coles, Easton, Pa., assignors to General Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware No Drawing. Application December 23, 1947, Serial No. 793,533

5 Claims The present invention relates to the production of phenazonium dyestufi images by color development of exposed silver halide emulsions by means of derivatives of ortho-phenylene diam ine, and more particularly to the employment in such process of color formers which directly yield the phenazonium dyestufi images by such color development.

Schmidt and Tulagin copending' application Ser. No. 640,382, filed January 10, 1946, now Patent No. 2,486,440, describes the production of phenazonium dyestuff images by color developing an exposed silver halide emulsion with a color developer comprising a developer of the orthophenylene diamine type in the presence of 8- hydroxy-quinoline as the color former.

'The phenazonium dye images produced in this way are extremely desirable from the standpoint of transmission spectra and stability. However, the phenazonium dyes of such images are only formed by a special after-treatment with acids or alkalies of the green dye image, presumably of a quinoneimine, resulting from the color forming development step. The value of the phenazonium dye as a photographic image is therefore somewhat ofiset by the fact that additional time and chemicals are necessary in order to obtain the image thereof.

It has now been found-that such dye images can be directly produced by the color forming development step, i. e., without an additional after-treatment if there be employed as the color former B-hydroxy-quinolines (including 8-hydroxy cinchomnic acids) containing in the 6 position of the quinoline ring a substituent which is eliminated during the color forming development as a negative ion. The utilization of such color formers in the production of phenazonium dyestufi images and silver halide emulsions containing the same accordingly constitute the purposes and objects of the present invention.

The color formers contemplated herein are characterized by the following general formula: I

wherein R is halogen, i. e.,-bromine, chlorine, iodine, or the like, nitro, sulfo, or an arsonic acid radical, R1 is hydrogemalkyl or a mononuclear carb cyc ic a ma c rad cal such as phenyl, i

nitrophenyl, aminophenyl, stearoylaminophenyl, octadecanesulfonamidophenyl, chlorophenyl, tolyl, anisyl and the like, R2 is hydrogen, -COOH or --CONHR3 and R3 is a sulfonated aliphatic 5 radical containingat least carbon atoms or a sulfonated aromatic radical substituted by an aliphatic radical containing at least 10 carbon atoms.

Examples of compounds embraced by the above 10 formula are the following:

6-bromo-8-hydroxyquin0line SOQH I OH 6-sulfo-8-hydroxyquinoline moms-m 6-arsono-s-hydroxyquinoline OzN I N CH 6-nitro-8-hydroxyquinoline 40 5. v COzH 2-phenyl-6-bromo-8-hydroxycinchoninic acid 6. CODE 6sulfo-S-hydroxyclnchoninic acid Br- IYHS-CmHu N i 6-chloro-8-hydroxyquinoline 0H 8 2- (3-octade canesulfonamidqpheny l) -6-bromo-8- Br hydr'oxycinchoumle acid 10 16. C 0 OH CH3 1 N 6-bromo-8-hydroxyquinaldine 2&(4-ohldroph'eny1I-6-bromo'8-hydroxycinch0ninic acid 17. C O OH 6-stearoylamino-2-(2-pheny1-6-bromo-8-l1ydrpxycinchoninoyl) aminotoluene -sulfonlc acid 18.

---N-UuaHa1v 2-'(4-methoxypheny1) -'6-'br0mo-8-hydroxycinchoninic acid 1 It willbe apparentthat in thecompounds listed- 2-phenyl-6-ch10ro-8-hydroxycinchoninoyloctadecyltaurine above, those containingvthe Ilongaliphatianhain W Wil1 .-be-;n0n.-.migratory when located in. photographic emulsions. Consequentlywhen the em- AT-N, ploymentof these compounds is desired, they are 40 most. advantageously dispersed in emulsions.

OC10Hn Theiothercompounds, however, may be employed.

either. in ,the developer or in the emulsion-a1-v AOSH though it ispreferred thatthey be added-to the.

developer.

The color vdeveloperswvhichare utilized are, as

stated, of-thezortho-phenylene diamine type,. a

large numberv of example .of which are referred 6-decoxy-3-(2-pl1e11yl-6-br0mo-8-hydroxycinch0ninoy1)- to in the aforesaid Schmidt and Tu1aginappli-- ammobenzenesulfomc and cation. Suitable developers of thisclass are, for 00 OH 0. example:

4,6 diani1ino-metanilic acid 4-(o-methoxy phenylamino) 6 (p methoxy- 55, phenylamino) -metani1ic acid 4,6-'bis-(o-methoxy phenylamino) -metanilic acid 4- (p-sulfo-phenylamino) -6 dimethylamino-metanilic acid.

and. .the. like: Many of i the: color formers "previously referred to are .known' compounds. Those which are not describedin. the literature, such as compounds 9 tov 18;.areprepared by methods conventional in the art. For instance, compound No. 9 may be 2 obtained by treating equimolecular quantities of 2- -(B-ammophenyl)-6-bromo-8-hydroxycmchomnlc acid phenyl 6 bromo s hydroxycinchoninic acid and 14. 00 6-amino-2-stearoylaminotoluene-4-sulfonic acid 0 in pyridine solution ,with an excess of phosphorus Br NBA-017E trichloride. Compounds'10...and 11 can be prel r pared by similar procedures-using the appropriate intermediates. N Compound 7 12can be-prepared by heating a H mixture of I 2=amino-5-bromophenol, m-nitrobenzaldehyde and pyruvic acid in ethyl alcohol. 2 (3 iiligifi figfi i ifii $3 8 C poun -1 c be p p ed by y o e a in 2- (3-nitrophenyl) -6-bromo-8-hydroxycinchoninic acid 13. C O O H i IIIH:

4,6-bis-. (mmethoxy-phenylamino) -metanilic acid compound 12 dissolved in aqueous sodium hydroxide using a platinum oxide catalyst. Compounds 14 and 15 can be prepared by reacting compound 13 in pyridine solution with octadecanoyl chloride and octadecanesulfonyl chloride respectively. Compounds 16, 17 and 18 can be prepared by employing the procedure described for compound 12 using p-chlorobenzaldehyde, pmethylbenzaldehyde and p-methoxybenzaldehyde respectively in place of m-nitrobenzaldehyde.

The invention is illustrated by the following examples, but it is to be understood that these examples are illustrative and not limitative of the invention.

Example 1 A photographic silver bromide emulsion is exposed and then color developed for 5 to minutes in a solution of the following color developer:

Sodium carbonate monohydrate grams 60 Potassium bromide do-.. 2 Sodium sulfite do 40 Pyridine cc 12 4,6-dianilino-metanilic acid grams 4 6-bromo-8-hydroxyquinoline do 2 Water cc 1000 A magenta phenazonium dyestuff image is directly produced by this development. By further processing the film in the usual manner, images of an excellent transmission spectra and stability are obtained.

Example 2 .5 gram of compound No. 9 is dissolved in 1.4 ml. of 0.05 N-lithium hydroxide, the solution diluted to 17 ml. with water and then neutralized with dilute acetic acid. The resulting solution is added to 35 grams of a photographic silver bromide emulsion and the emulsion coated on a film base.

The emulsion is then exposed and color developed with the developer of Example 1, excepting that the 6-bromo-8-hydroxyquinoline is omitted therefrom. A brilliant magenta phenazonium dyestuff image of excellent stability is directly produced in the development step.

Various modifications of the invention will occur to workers in this art, and we therefore do not intend to be limited in the patent granted except as necessitated by the prior art and the appended claims.

We claim:

1. The process of producing magenta phenazonium dyestuif images by color forming development which comprises exposing a silver halide emulsion and developing the same with a 2,4- diaminoaniline developer in the presence of a color former having the following formula:

wherein R is a member of the class consisting of halogen, nitro, sulfo and arsonic acid radicals, R1 is a member of the class consisting of hydrogen, alkyl and a mononuclear carbocyclic aromatic radical, R2 is a member of the class consisting of H, -COOH and CONHR3 and R3 is a member selected from the class consisting of sulfonated aliphatic radicals containing at least 10 carbon atoms, and sulfonated aromatic radicals substituted by an aliphatic radical containing at least 10 carbon atoms.

2. The process as defined in claim 1 wherein the color former is 6-sulfo-8-hydroxy quinoline.

3. The process as defined in claim 1 wherein the color former is 6-bromo-8-hydroxy-quinoline.

4. A photographic silver halide emulsion containing as a color former capable of directly yielding magenta phenazonium dyestuif images when color developed with a 2,4-diamino aniline developer, a compound of the following formula:

wherein R. is a member of the class consisting of halogen, nitro, sulfo and arsonic acid radicals, R1 is a member of the class consisting of hydrogen, alkyl and a mononuclear carbocyclic aromatic radical, R2 is a member of the class consisting of H, COOH and --CONH-Ra and R3 is a member selected from the class consisting of sulfonated aliphatic radicals containing at least 10 carbon atoms, and sulfonated aromatic radicals substituted by an aliphatic radical containing at least 10 carbon atoms.

5. A photographic silver halide emulsion containing as a color former a compound of the following formula:

VSEVOLOD TULAGIN. ROBERT F. COLES.

REFERENCES CITED The following references are of record in the file of this patent:

FOREIGN PATENTS 

1. THE PROCESS OF PRODUCING MAGENTA PHENAZONIOUM DYESTUFF IMAGES BY CCOLOR FORMING DEVELOPMENT WHICH COMPRISES EXPOSING A SILVER HALIDE EMULSION AND DEVELOPING THE SAME WITH A 2,4DIAMINOANILINE DEVELOPER IN THE PRESENCE OF A COLOR FORMER HAVING THE FORMULA: 